西班牙加泰罗尼亚纳米科学和纳米技术研究所Daniel Maspoch团队报道了基于铑(II)‐基于金属–有机多面体的金属配位位阻驱动吡啶区域异构体的分离。 相关研究成果于2021年2月23日发表在出版的《德国应用化学》。
异构体的物理化学相似性使得它们通过传统技术进行化学分离需要大量的能源。
该文中,研究人员开发了一种能够取代传统的封装驱动工艺,Rh(II)基金属有机多面体(Rh-MOPs)外表面金属配位中的空间位阻可用于通过液-液萃取分离吡啶基区域异构体。通过分子动力学模拟和湿实验,研究人员发现吡啶与Rh-MOPs的配位结合能力取决于吡啶取代基相对于吡啶氮的位置,并受空间位阻的影响。因此,研究人员利用结合和非结合吡啶区域异构体的不同溶解度来设计液-液自分选系统。
为了验证方案的有效性,研究人员分离了四种不同的区域异构体等分子混合物,包括工业相关化合物2-氯吡啶和3-氯吡啶的混合物,在所有情况下均分离出高纯度的化合物。
附:英文原文
Title: Steric Hindrance in Metal Coordination Drives the Separation of Pyridine Regioisomers Using Rhodium(II)‐Based Metal–Organic Polyhedra
Author: Laura Hern, Jordi Martí, Arnau Carn, Thais Grancha, Jordi Faraudo, Daniel Maspoch
Issue&Volume: 2021-02-23
Abstract: The physicochemical similarity of isomers makes their chemical separation through conventional techniques energy intensive. Herein, we report that, instead of using traditional encapsulation‐driven processes, steric hindrance in metal coordination on the outer surface of Rh(II)‐Based Metal Organic Polyhedra (Rh‐MOPs) can be used to separate pyridine‐based regioisomers via liquid‐liquid extraction. Through molecular dynamics simulations and wet experiments, we discovered that the capacity of pyridines to coordinatively bind to Rh‐MOPs is determined by the positions of the pyridine substituents relative to the pyridine nitrogen and is influenced by steric hindrance. Thus, we exploited the differential solubility of bound and non‐bound pyridine regioisomers to engineer liquid‐liquid self‐sorting systems. As proof‐of‐concept, we separated four different equimolecular mixtures of regioisomers, including a mixture of the industrially‐relevant compounds 2‐chloropyridine and 3‐chloropyridine, isolating highly pure compounds in all cases.
DOI: 10.1002/anie.202100091
Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202100091
Angewandte Chemie:《德国应用化学》,创刊于1887年。隶属于德国化学会,最新IF:12.959
官方网址:https://onlinelibrary.wiley.com/journal/15213773
投稿链接:https://www.editorialmanager.com/anie/default.aspx